Curable composition, cured product, and laminate

Abstract

To provide a curable composition that enables both formation of a fine irregular surface structure on a cured product and expression of matte properties, as well as curing under a lowered irradiation dose of active energy rays, and to provide a cured product of the curable composition and a laminate including a layer composed of the cured product.SOLUTION: A curable composition comprises a polymer having an active group that generates radicals upon irradiation with active energy rays, a non-polymer photopolymerization initiator, and a (meth)acrylate.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a curable composition, a cured product of the curable composition, and a laminate including the cured product layer.

Background Art

[0002] As a method for imparting a matte property and improving the design and visibility by forming a fine concavo-convex structure on the surface of a substrate, for example, a method of applying a curable composition in which fine particles are dispersed to the substrate and curing it, a method of depositing a thin film of metal on the substrate, and a method of developing fine wrinkles on the surface of a cured product obtained by applying a curable composition to the substrate and curing it are known.

[0003]

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, in the case of the method of Patent Document 1, depending on the composition, it is necessary to increase the amount of active energy ray irradiation for curing. In this case, for example, there is a possibility that a sufficient concavo-convex structure is not formed and the optical properties are inferior, or there is a possibility of insufficient curing when the processing speed is increased.

[0006] ​The present invention has been made to improve the above problems, and has a fine uneven structure on the surface of the cured product to form, exhibit matting properties, and enable curing even when the irradiation amount of active energy rays is low and an object of the present invention is to provide a curable composition capable of increasing the processing speed.

Means for Solving the Problems

[0007] The present invention has the following aspects. [1] A curable composition containing a polymer having an active group that generates radicals upon irradiation with active energy rays, a photoinitiator for non-polymer merization, and (meth)acrylate. [2] The active group that generates radicals upon irradiation with the active energy rays is α-hydroxy ketone group, benzophenone group, acetophenone group, benzoin group, α-aminoketone group , α-diketone group, α-diketone dialkyl acetal group, anthraquinone group, thiox anthone group, and phosphine oxide group, and is one or more selected from the group consisting of the above [1 curable composition. [3] The polymer having an active group that generates radicals upon irradiation with the active energy rays is , a perfluoroalkylene group, or a (meth)acryl alkyl ester having an alkyl group having 4 or more carbon atoms, and the curable composition of the above [1] or [2]. [4] The weight average molecular weight of the polymer having an active group that generates radicals upon irradiation with the active energy rays is 1000 to 500000, and the curable composition of the above [1] to [3]. [5] The molecular weight of the photoinitiator for non-polymer is less than 1000, and the curable composition of the above [1] to [4 . [6] The photoinitiator for non-polymer is of the alkylphenone type or benzyl ketal type and the curable composition of the above [1] to [5].​ [7] The curable composition according to any one of [1] to [6], wherein the (meth)acrylate has a functionality of 3 or more. Composition. [8] The curable composition according to any one of [1] to [7], wherein the (meth)acrylate contains at least one selected from the group consisting of urethane acrylate, (meth)acrylate of a hyperbranched polymer, and glycerin-containing (meth)acrylate. Containing. Composition. [9] A cured product obtained by curing the curable composition according to any one of [1] to [8].

[10] The cured product according to [9], wherein the cured product is a film having an uneven structure on the surface.

[11] The cured product according to [9] or

[10] , wherein the haze of the cured product is 3% or more.

[12] The cured product according to any one of [9] to

[11] , wherein the 20° gloss of the cured product is 80 or less. Product.

[13] The cured product according to any one of [9] to

[0012] , wherein the arithmetic mean roughness (Ra) of the cured product is 0.01 μm or more.

[14] A method for producing a cured product, comprising forming a coating film of a curable composition containing a polymer having an active group that generates radicals upon irradiation with active energy rays, a photopolymerization initiator for non-polymerizable monomers, and (meth)acrylate, and irradiating the coating film with active energy rays. And forming. Coating film, and irradiating the coating film with active energy rays.

[15] A laminate obtained by laminating the cured product according to any one of [9] to

[13] on a substrate surface. [Advantages of the Invention]

[0008] According to the present invention, there can be provided a curable composition that cures even with a low irradiation amount of active energy rays, a cured product obtained by curing the curable composition and having a matting property, and a laminate obtained by laminating the cured product on the surface of a substrate. And laminating. Body. [Embodiments for Carrying Out the Invention]

[0009] Hereinafter, embodiments of the present invention will be described in detail. In the present invention, "(meth)acrylate" is a general term for acrylate or methacrylate. The term is used to refer to the total of acrylate and methacrylate. The symbol "~" indicating a numerical range means that the numerical values described before and after it are included as the lower limit value and the upper limit value. The numerical ranges disclosed in this specification can be combined arbitrarily with the lower limit value and the upper limit value to form a new numerical range.

[0010] <Curable Composition> The curable composition of the present invention contains a polymer having an active group that generates radicals upon irradiation with active energy rays, a non-polymeric photoinitiator, and (meth)acrylate.

[0011] <Polymer Having an Active Group That Generates Radicals upon Irradiation with Active Energy Rays> The active group in the polymer having an active group that generates radicals upon irradiation with active energy rays is a group having a structure that generates radicals upon irradiation with active energy rays, in other words, a structure having photoinitiation properties. Examples of the structure having photoinitiation properties include hydrogen abstraction type, electron transfer type, and intramolecular cleavage type. In the present invention, the radicals generated from the active group react with (meth)acrylate to form a crosslinked structure.

[0012] Examples of the active group include an α-hydroxyketone group (for example, a group obtained by removing one hydrogen atom from the "hydroxyl group in 2-hydroxyethoxy" of 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-methylpropanone), a benzophenone group, an acetophenone group, a benzoin group, an α-aminoketone group, an α-diketone group, an α-diketone dialkylacetal group, an anthraquinone group, a thioxanthone group, and a phosphine oxide group. Among these, those that are less susceptible to oxygen inhibition during curing and have good surface curability when forming the uneven layer are preferred in terms of being good, such as α-hydroxy ketone groups, benzophenone groups, and acetophenone groups.

[0013] The active group may be present at the end of the main chain of the polymer or may be present in the constituent units derived from the monomers constituting the polymer. The polymer can increase the concentration of the active group near the coating surface and is less susceptible to oxygen inhibition, so it is preferable to improve the curability and to easily develop an uneven structure such as a wrinkled structure on the surface after curing. Therefore, it is preferable to have a plurality of active groups in the molecule.

[0014] As the polymer having a plurality of active groups, a polymer having a constituent unit derived from a monomer having an active group is preferred. Examples of the monomer having an active group include compounds having an active group and a radical polymerizable group. Examples of the radical polymerizable group include functional groups containing a radical polymerizable unsaturated bond such as a carbon-carbon double bond. Specific examples include (meth)acryloyl groups, (meth) acrylamide groups, vinyl groups, and the like.

[0015] From the viewpoints of ease of polymer synthesis and ease of adjusting the introduction amount of the active group, (meth)acrylate esters are preferred as the monomer having an active group. For example, 2-[4-(2- hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate, 4 -methacryloyloxybenzophenone, and the like can be mentioned.

[0016] The ratio of the constituent unit derived from the monomer having an active group to the total mass of all the units constituting the polymer is preferably 1 to 90% by mass, more preferably 5 to 80% by mass, still more preferably ... ​​It is in the range of 15 to 70% by mass, particularly preferably 30 to 60% by mass. If this ratio is within the above range, the curability can be improved and the uneven structure can be effectively formed. Within this range, the curability can be improved and the uneven structure can be effectively formed.

[0017] In the polymer having an active group that generates radicals by irradiation with active energy rays, in addition to the structural unit derived from the monomer having an active group, it preferably has a perfluoroalkylene group or a structural unit derived from a monomer having an alkyl group with 4 or more carbon atoms, and more preferably it is a perfluoroalkylene group. If the polymer has this unit, when forming a coating film of the curable composition, the polymer is likely to segregate to the surface side of the coating film. Due to such segregation, the curing reaction inside the coating film (substrate side) is less likely to be inhibited by oxygen, and the curability is improved. For example, it can be cured with a low irradiation amount, and even a thin coating film that tends to be inhibited by oxygen can be cured well. In addition to the structural unit derived from the monomer having an active group, it preferably has a perfluoroalkylene group or a structural unit derived from a monomer having an alkyl group with 4 or more carbon atoms, and more preferably it is a perfluoroalkylene group. If the polymer has this unit, when forming a coating film of the curable composition, the polymer is likely to segregate to the surface side of the coating film. Due to such segregation, the curing reaction inside the coating film (substrate side) is less likely to be inhibited by oxygen, and the curability is improved. For example, it can be cured with a low irradiation amount, and even a thin coating film that tends to be inhibited by oxygen can be cured well. In addition to the structural unit derived from the monomer having an active group, it preferably has a perfluoroalkylene group or a structural unit derived from a monomer having an alkyl group with 4 or more carbon atoms, and more preferably it is a perfluoroalkylene group. If the polymer has this unit, when forming a coating film of the curable composition, the polymer is likely to segregate to the surface side of the coating film. Due to such segregation, the curing reaction inside the coating film (substrate side) is less likely to be inhibited by oxygen, and the curability is improved. For example, it can be cured with a low irradiation amount, and even a thin coating film that tends to be inhibited by oxygen can be cured well. In addition to the structural unit derived from the monomer having an active group, it preferably has a perfluoroalkylene group or a structural unit derived from a monomer having an alkyl group with 4 or more carbon atoms, and more preferably it is a perfluoroalkylene group. If the polymer has this unit, when forming a coating film of the curable composition, the polymer is likely to segregate to the surface side of the coating film. Due to such segregation, the curing reaction inside the coating film (substrate side) is less likely to be inhibited by oxygen, and the curability is improved. For example, it can be cured with a low irradiation amount, and even a thin coating film that tends to be inhibited by oxygen can be cured well. In addition to the structural unit derived from the monomer having an active group, it preferably has a perfluoroalkylene group or a structural unit derived from a monomer having an alkyl group with 4 or more carbon atoms, and more preferably it is a perfluoroalkylene group. If the polymer has this unit, when forming a coating film of the curable composition, the polymer is likely to segregate to the surface side of the coating film. Due to such segregation, the curing reaction inside the coating film (substrate side) is less likely to be inhibited by oxygen, and the curability is improved. For example, it can be cured with a low irradiation amount, and even a thin coating film that tends to be inhibited by oxygen can be cured well. In addition to the structural unit derived from the monomer having an active group, it preferably has a perfluoroalkylene group or a structural unit derived from a monomer having an alkyl group with 4 or more carbon atoms, and more preferably it is a perfluoroalkylene group. If the polymer has this unit, when forming a coating film of the curable composition, the polymer is likely to segregate to the surface side of the coating film. Due to such segregation, the curing reaction inside the coating film (substrate side) is less likely to be inhibited by oxygen, and the curability is improved. For example, it can be cured with a low irradiation amount, and even a thin coating film that tends to be inhibited by oxygen can be cured well. In addition to the structural unit derived from the monomer having an active group, it preferably has a perfluoroalkylene group or a structural unit derived from a monomer having an alkyl group with 4 or more carbon atoms, and more preferably it is a perfluoroalkylene group. If the polymer has this unit, when forming a coating film of the curable composition, the polymer is likely to segregate to the surface side of the coating film. Due to such segregation, the curing reaction inside the coating film (substrate side) is less likely to be inhibited by oxygen, and the curability is improved. For example, it can be cured with a low irradiation amount, and even a thin coating film that tends to be inhibited by oxygen can be cured well. In addition to the structural unit derived from the monomer having an active group, it preferably has a perfluoroalkylene group or a structural unit derived from a monomer having an alkyl group with 4 or more carbon atoms, and more preferably it is a perfluoroalkylene group. If the polymer has this unit, when forming a coating film of the curable composition, the polymer is likely to segregate to the surface side of the coating film. Due to such segregation, the curing reaction inside the coating film (substrate side) is less likely to be inhibited by oxygen, and the curability is improved. For example, it can be cured with a low irradiation amount, and even a thin coating film that tends to be inhibited by oxygen can be cured well.

[0018] As the perfluoroalkylene group, conventionally known compounds can be used. For effective formation of the uneven structure, the number of carbon atoms of the perfluoroalkylene group is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and most preferably 6 or more. The upper limit is not particularly limited, but preferably it is 30. As the perfluoroalkylene group, conventionally known compounds can be used. For effective formation of the uneven structure, the number of carbon atoms of the perfluoroalkylene group is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and most preferably 6 or more. The upper limit is not particularly limited, but preferably it is 30. As the perfluoroalkylene group, conventionally known compounds can be used. For effective formation of the uneven structure, the number of carbon atoms of the perfluoroalkylene group is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and most preferably 6 or more. The upper limit is not particularly limited, but preferably it is 30. As the perfluoroalkylene group, conventionally known compounds can be used. For effective formation of the uneven structure, the number of carbon atoms of the perfluoroalkylene group is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and most preferably 6 or more. The upper limit is not particularly limited, but preferably it is 30.

[0019] Also, from the viewpoint of forming the surface uneven structure, the perfluoroalkylene group is preferably a terminal structure rather than an internal structure. Compared with making it an internal structure, making it a terminal structure allows it to be unevenly distributed on the surface when cured, and a more effective uneven structure can be formed. Also, from the viewpoint of forming the surface uneven structure, the perfluoroalkylene group is preferably a terminal structure rather than an internal structure. Compared with making it an internal structure, making it a terminal structure allows it to be unevenly distributed on the surface when cured, and a more effective uneven structure can be formed. Also, from the viewpoint of forming the surface uneven structure, the perfluoroalkylene group is preferably a terminal structure rather than an internal structure. Compared with making it an internal structure, making it a terminal structure allows it to be unevenly distributed on the surface when cured, and a more effective uneven structure can be formed.

[0020] The terminal of the perfluoroalkylene group includes a hydrogen atom or a halogen atom. Among them, a hydrogen atom or a fluorine atom is preferable, and a fluorine atom (i.e., a perfluoro alkyl group) is more preferable. By using a perfluoroalkyl group, all atoms bonded to carbon become fluorine atoms, so it tends to be unevenly distributed on the surface, and the compatibility with other materials may also decrease, making it excellent in forming a surface uneven structure. In addition, it can also be made to have excellent antifouling properties

[0021] and liquid repellency. Also, the perfluoroalkylene group may be linear, for example, it may have a branched chain such as a perfluoroisopropyl group. From the viewpoint of being excellent in forming a surface

[0022] uneven structure, a linear one is preferable. That is, as the optimal structure of the perfluoroalkylene group, it is a perfluoroalkylene group having 6 or more carbon atoms, for example, a perfluorohexyl group, a perfluorohexylene group, etc. can be mentioned. These perfluoroalkylene groups may be used alone or in combination

[0023] of two or more. ,1H,7H-dodecafluoromethyl heptyl methacrylate (manufactured by Daikin Industries, Ltd.) 2, 2,3,3-tetrafluoropropyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Bis Coat 4F), 1H,1H,5H-octafluoropentyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Bis Coat 8F), 1H,1H,5H-octafluoropentyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Bis Coat 8FM), 1H,1H,2H,2H -tridecafluorooctyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., 3F), 1H,1H,2H,2H-nonafluorohexyl acrylate (Unimatec Co., Ltd., CHEMINOX FAAC-4), 1H,1H,2H,2H-nonafluorohexyl methacrylate (Unimatec Co., Ltd., CHEMINOX FAMAC-4) and 1H,1H,2H,2H-tridecafluorooctyl methacrylate (Unimatec Co., Ltd., CHEMINOX FAMAC-6) are commercially available, etc. As the monomer having an alkyl group with 4 or more carbon atoms, it may be linear, branched or cyclic. The cyclic alkyl group may be monocyclic or polycyclic. From the viewpoint of more effectively segregating the copolymer on the surface of the coating film, the alkyl group is preferably linear. From the viewpoint of more effectively segregating the polymer having 4 or more carbon atoms on the surface of the coating film, the carbon number of the alkyl group having 4 or more carbon atoms is preferably in the range of 4 to 30, more preferably in the range of 6 to 20, and still more preferably in the range of 12 to

[0024] 18. As the monomer, a compound having an alkyl group with 4 or more carbon atoms and a radically polymerizable group can be mentioned. From the viewpoints of ease of synthesis of the compound and ease of adjustment of the introduction amount of the alkyl group having 4 or more carbon atoms, alkyl (meth)acrylate having an alkyl group with 4 or more carbon atoms is preferred. For example, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, etc.

[0025] As the monomer, a compound having an alkyl group with 4 or more carbon atoms and a radically polymerizable group can be mentioned. From the viewpoints of ease of synthesis of the compound and ease of adjustment of the introduction amount of the alkyl group having 4 or more carbon atoms, alkyl (meth)acrylate having an alkyl group with 4 or more carbon atoms is preferred. For example, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate,

[0026] lauryl (meth)acrylate, stearyl (meth)acrylate, etc. acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, etc. Sil (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate -, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth ) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, ste aryl (meth) acrylate, isostearyl (meth) acrylate, tridecyl (meth ) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, tricyclode cane (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl ( meth) acrylate, adamantyl (meth) acrylate and the like can be mentioned. Among these, it is preferable to contain an alkyl (meth) acrylate having a linear alkyl group with 4 or more carbon atoms. Among these, it is preferable to contain an alkyl (meth) acrylate having a linear alkyl group with 4 or more carbon atoms. ) As the alkyl (meth) acrylate, those having the number of carbon atoms of the alkyl group within the above-mentioned preferable range are preferable. Considering ease of production and the like, 2-ethylhexyl (meth) acry late, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl ( meth) acrylate are more preferable, and stearyl (meth) acrylate is particularly preferable. These (meth) acrylic acid esters may be used alone or in combination of two or more. These (meth) acrylic acid esters may be used alone or in combination of two or more. It may be used.

[0027] The ratio of the constituent unit derived from a monomer having a perfluoroalkylene group or an alkyl group having 4 or more carbon atoms to the total mass of all the constituent units constituting the polymer having an active group that generates radicals by irradiation with active energy rays is preferably 80% by mass or less, more preferably 1 ~70% by mass, still more preferably 5~60% by mass, particularly preferably 10~55% by mass range is. ~70% by mass, still more preferably 5~60% by mass, particularly preferably 10~55% by mass range It is a circle. If this ratio is within the above range, the surface uneven structure can be effectively formed.

[0028] Further, instead of the structural unit derived from a monomer having a perfluoroalkylene group or an alkyl group having 4 or more carbon atoms, or in addition, it may have a structural unit derived from a monomer containing a silicon atom. For the monomer containing a silicon atom, (meth)acrylate containing a silicon atom is preferable, and (meth)acrylate having a polydimethylsiloxane chain is more preferable. As a specific example of the (meth)acrylate having a polydimethylsiloxane chain, one-terminal (meth)acryloyl group-substituted polydimethylsiloxane having a molecular weight of 500 to 50,000 can be mentioned. The above molecular weight is preferably 1,000 to 30,000, and more preferably 1,500 to 20,000. The polymer having an active group that generates radicals by irradiation with active energy rays may optionally have a structural unit derived from a monomer having a hydrogen-donating functional group. Particularly when the active group includes a hydrogen-abstraction type, it preferably includes a structural unit derived from a monomer having a hydrogen-donating functional group. If the polymer has this unit, the coating film of the curable composition is effectively cured from the surface, so the curability is improved and the uneven structure is easily formed. Examples of the hydrogen-donating functional group include a hydroxyl group, an amino group, a mercapto group, and an amide group. Among these, from the viewpoints of particularly efficiently proceeding the curing reaction, improving the curability, or easily forming the uneven structure, a hydroxyl group, an amino group, or an amide group is preferable.

[0029]

[0029]

[0030] Examples of the monomer having a hydrogen-donating functional group include compounds having a hydrogen-donating functional group and a radical polymerizable group. From the viewpoints of ease of synthesizing the compound and ease of adjusting the introduction amount of the hydrogen-donating functional group, (meth)acrylate having a hydrogen-donating functional group is preferable. Examples of the monomer having a hydrogen-donating functional group include, for example, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, monobutylhydroxyl fumarate, monobutylhydroxyitaconate and other hydroxyl group-containing monomers; N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-vinylcaprolactam, N-vinylpyrrolidone, N-isopropyl (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, 2-[(butylamino)carbonyl]oxy]ethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, (meth)acryloylmorpholine, vinylacetamide and other amino group- or amide group-containing monomers. Among them, 2-hydroxyethyl ( (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybut (meth)acrylate, (N,N-dimethylacrylamide, N,N-dimethylami noethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate are preferred. In terms of being easy to increase the uneven structure, N,N-diethylaminoethyl (meth )acrylate is more preferred. These compounds may be used alone or in combination of two or more .

[0031] The ratio of the structural unit derived from the monomer having a hydrogen-donating functional group to the total mass of all units constituting the polymer is preferably 80% by mass or less, more preferably 1 to 40% by mass, still more preferably 3 to 35% by mass, and particularly preferably in the range of 5 to 30% by mass. If this ratio is within the above range, the curability can be improved and the uneven structure can be effectively formed.

[0032] The polymer having an active group that generates radicals by irradiation with active energy rays may, if necessary, further have a structural unit derived from other monomers other than the above. Examples of other monomers include compounds having a radical polymerizable group and not having an active group, a perfluoroalkylene group, an alkyl group having 4 or more carbon atoms, a silicon atom, or a hydrogen-donating functional group. Examples of other monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, citraconic acid and their salts; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate to etc. (meth)acrylate; nitrogen-containing monomers such as (meth)acrylonitrile; styrene ​​​ , styrene compounds such as α-methylstyrene, divinylbenzene, vinyltoluene; pro pionate vinyl, vinyl acetate and other vinyl esters; γ-methacryloxypropyltrimeth oxysilane, vinyltrimethoxysilane and other silicon-containing monomers; phosphorus-containing vinyl monomers; salt vinyl chloride, vinylidene chloride and other vinyl halides; conjugated dienes such as butadiene are included .

[0033] The weight average molecular weight (Mw) of the polymer having an active group that generates radicals upon irradiation with active energy rays is preferably in the range of 1,000 to 500,000, more preferably 3,000 to 300,000, and even more preferably 5,000 to 200,000. If Mw is within the above range, the coatability and curability of the curable composition are further improved, and the tendency to form an uneven structure is more improved. The Mw of the polymer is a value in terms of standard polystyrene measured by gel permeation chromatography (GPC). The detailed measurement conditions are as described in the examples below .

[0034] The content of active groups per gram of the polymer having an active group that generates radicals upon irradiation with active energy rays is preferably 0.1 to 3.5 mmol / g, more preferably 0.3 to 3.0 mmol / g, even more preferably 0.5 to 2.7 mmol / g, particularly preferably 1 .0 to 2.5 mmol / g. If the content of active groups is within the above range, the curability is more excellent and unevenness can be formed more effectively.

[0035] The polymer having an active group that generates radicals upon irradiation with active energy rays is typically ​​​It can be produced by polymerizing a monomer as a raw material in the presence of a polymerization initiator. During the polymerization, if necessary, a chain transfer agent may be used in combination. Examples of the polymerization method include solution polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization. Among them, solution polymerization is preferred in terms of simple operation and high productivity.

[0036] <Non-polymeric photoinitiator> In addition to polymers having an active group that generates radicals upon irradiation with active energy rays, a non-polymeric photoinitiator is incorporated into the curable composition, so that a cured product can be obtained even with a low irradiation dose of active energy rays. A non-polymeric photoinitiator refers to a photoinitiator that has not polymerized, and examples thereof include monomolecular photoinitiators. Among them, a compound having a molecular weight of less than 1,000 is preferred because it can be uniformly and easily dispersed in the curable composition, and more preferably 500 or less. Examples of the photoinitiator include photo radical polymerization initiators, photo cationic polymerization initiators, photo anionic polymerization initiators, etc. Among these, photo radical polymerization initiators are preferred. Examples of the photo radical polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxyl)-phenyl]-2-hydroxy-2-methylpropanone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1- propanone, etc.

[0037] ​​​​​​​​​- Alkylphenone type compounds such as propanone, 2,2 - dimethoxy - 2 - phenylacet Benzyl ketal type compounds such as phenone, benzophenone, 4 - methylbenzophenone, 2,4,6 - trimethylbenzophenone, methyl orthobenzoylbenzoate, 4 - f Benzophenone type compounds such as enylbenzophenone; t - butylanthraquinone, 2 - e Anthraquinone type compounds such as thylanthraquinone; 2 - benzyl - 2 - dimethylamino - 1 - (4 - morpholinophenyl) - butanone - 1, diethylthioxanthone, isoprop Thioxanthone type compounds such as ylthioxanthone; 2,4,6 - trimethylbenzoyldif Enylphosphine oxide, bis(2,6 - dimethoxybenzoyl) - 2,4,4 - t Rimethylpentylphosphine oxide, bis(2,4,6 - trimethylbenzoyl) - Acylphosphine oxide type compounds such as phenylphosphine oxide; phenylg Examples include phenylglyoxylate type compounds such as lyoxylic acid methyl ester. Among these, in terms of curing even with a small amount of active energy ray irradiation, an Alkylphenone type compound or benzyl ketal type compound is preferable, and an alkylphenone Type compound is more preferable. Among alkylphenone type compounds, α - hydroxy a Lkylphenone type compounds and α - aminoalkylphenone type compounds are preferable, and α - hydro Xyalkylphenone type compounds are more preferable, and among them, 1 - hydroxycyclohe Xylphenyl ketone, or 2 - hydroxy - 1 - {4 - [4 - (2 - hydroxy - 2 - methylpropionyl)benzyl]phenyl} - 2 - methylpropane - 1 - one is further Preferred, and 1 - hydroxycyclohexylphenyl ketone is most preferred. Also, these ​ The polymerization initiator may be used alone or in combination of two or more kinds.

[0038] <(meth)acrylate> There are no particular limitations on the (meth)acrylate, and one or more of monofunctional (meth)acrylates, bifunctional (meth)acrylates, trifunctional or higher polyfunctional (meth)acrylates mixed together, those commercially available as curable resin materials, or those obtained by further adding other components within the range not impairing the object of the present embodiment can be used. Among these, from the viewpoint of excellent curability, trifunctional or higher polyfunctional (meth)acrylates are preferable, and hexafunctional or higher polyfunctional (meth)acrylates are more preferable.

[0039] Examples of the monofunctional (meth)acrylate include methyl (meth)acrylate, ethyl (meth) acrylate, butyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, morpholyl (meth) acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl ( meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth) acrylate, tricyclodecane (meth)acrylate, polyethylene glycol mono (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, etc. (Meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (Meth)acrylate, isobornyl (meth)acrylate, allyl (meth)acrylate -ate, 2-ethoxyethyl (meth)acrylate, benzyl (meth)acrylate, phen oxyethyl (meth)acrylate, phenyl (meth)acrylate, etc. of mono(meth)a crylate, adducts of phthalic anhydride and 2-hydroxyethyl (meth)acrylate, etc. of mono(meth)acrylate compounds and the like can be mentioned.

[0040] As the bifunctional and polyfunctional (meth)acrylates, although not particularly limited, for example 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth) acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanedi ol di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate and the like of alkanediol di(meth)acrylate, bisphenol A ethylene oxide modified di(meth)acrylate, bisphenol F ethylene oxide modified di(meth)acry late and the like of bisphenol modified di(meth)acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol di(meth)acrylate, urethane di(meth) acrylate, epoxy di(meth)acrylate and the like can be mentioned.

[0041] As the trifunctional or higher polyfunctional (meth)acrylates, although not particularly limited, for example dipentaerythritol hexa(meth)acrylate, pentaerythritol tet ra(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethyl Roll propanetetra(meth)acrylate, pentaerythritol tri(meth)acrylate rate, trimethylolpropane tri(meth)acrylate, glycerin triacrylate etc., glycerin-containing polyfunctional (meth)acrylates such as ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, etc., ethylene oxide-modified (meth)acrylates such as ethylene oxide-modified isocyanuric acid tri(meth)acrylate, isocyanuric acid-modified tri(meth)acrylates such as ε-caprolactone-modified tris(acryloxyethyl) isocyanurate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, etc. of urethane (meth)acrylate and the like can be mentioned. Among these, polyfunctional (meth)acrylates of 6 or more functional groups are preferable from the viewpoint of hardness, and furthermore, it is preferable that they are urethane (meth)acrylates from the viewpoint of adhesion to the substrate. Also, from the viewpoint that the uneven structure becomes fine and it becomes easier to adjust optical properties such as haze, glycerin-containing (meth)acrylate is preferable. Furthermore, hyperbranched (meth)acrylates can also be mentioned as polyfunctional (meth)acrylates. Although it is presumed that the mechanism is due to the random structure, using hyperbranched (meth)acrylates can reduce the appearance (non-uniformity) of the cured film. rate, etc. Among these, polyfunctional (meth)acrylates of 6 or more functional groups are preferable from the viewpoint of hardness, and furthermore, it is preferable that they are urethane (meth)acrylates from the viewpoint of adhesion to the substrate. Also, from the viewpoint that the uneven structure becomes fine and it becomes easier to adjust optical properties such as haze, glycerin-containing (meth)acrylate is preferable. ethylene oxide-modified isocyanuric acid tri(meth)acrylate, ε-caprolactone-modified tris(acryloxyethyl) isocyanurate, etc. of isocyanuric acid-modified tri(meth)acrylate, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, etc. of urethane (meth)acrylate and the like can be mentioned. Among these, polyfunctional (meth)acrylates of 6 or more functional groups are preferable from the viewpoint of hardness, and furthermore, it is preferable that they are urethane (meth)acrylates from the viewpoint of adhesion to the substrate. Also, from the viewpoint that the uneven structure becomes fine and it becomes easier to adjust optical properties such as haze, glycerin-containing (meth)acrylate is preferable. pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, etc. of urethane (meth)acrylate and the like can be mentioned. Among these, polyfunctional (meth)acrylates of 6 or more functional groups are preferable from the viewpoint of hardness, and furthermore, it is preferable that they are urethane (meth)acrylates from the viewpoint of adhesion to the substrate. Also, from the viewpoint that the uneven structure becomes fine and it becomes easier to adjust optical properties such as haze, glycerin-containing (meth)acrylate is preferable. pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, etc. of urethane (meth)acrylate and the like can be mentioned. Among these, polyfunctional (meth)acrylates of 6 or more functional groups are preferable from the viewpoint of hardness, and furthermore, it is preferable that they are urethane (meth)acrylates from the viewpoint of adhesion to the substrate. Also, from the viewpoint that the uneven structure becomes fine and it becomes easier to adjust optical properties such as haze, glycerin-containing (meth)acrylate is preferable. Polyfunctional (meth)acrylates of 6 or more functional groups are preferable from the hardness perspective, and furthermore, urethane (meth)acrylates are preferable from the adhesion perspective to the substrate. Also, from the perspective that the uneven structure becomes finer and it becomes easier to adjust optical properties such as haze, glycerin-containing (meth)acrylate is preferable. Furthermore, hyperbranched (meth)acrylates can also be mentioned as polyfunctional (meth)acrylates. Presumably due to the random structure, using hyperbranched (meth)acrylates can reduce the appearance (non-uniformity) of the cured film. Furthermore, hyperbranched (meth)acrylates can also be mentioned as polyfunctional (meth)acrylates. Presumably due to the random structure, using hyperbranched (meth)acrylates can reduce the appearance (non-uniformity) of the cured film. From the viewpoint that the uneven structure becomes fine and it becomes easier to adjust optical properties such as haze, glycerin-containing (meth)acrylate is preferable.

[0042] Furthermore, hyperbranched (meth)acrylates can also be mentioned as polyfunctional (meth)acrylates. Presumably due to the random structure, using hyperbranched (meth)acrylates can reduce the appearance (non-uniformity) of the cured film. Presumably due to the random structure, using hyperbranched (meth)acrylates can reduce the appearance (non-uniformity) of the cured film. Presumably due to the random structure, using hyperbranched (meth)acrylates can reduce the appearance (non-uniformity) of the cured film. It has also been found that it is possible.

[0043] In addition, it is also possible to use an active energy ray curable compound other than (meth)acrylate in the curable composition. For example, vinyl compounds such as styrene, vinyl halide, vinyl acetate, etc., diene compounds such as vinylidene halide, 1,3-butadiene, isoprene, chloroprene, etc. can be mentioned.

[0044] The curable composition may contain various polymers for adjusting the hardness when it becomes a cured product. For example, acrylic polymers, polyesters, polyurethanes, etc. can be mentioned.

[0045] In addition, the curable composition may contain an ultraviolet absorber in order to improve the weather resistance when it becomes a cured product. For example, organic ultraviolet absorbers and inorganic ultraviolet absorbers can be mentioned. From the viewpoints of transparency and compatibility, organic ultraviolet absorbers are preferred. The organic ultraviolet absorber is not particularly limited, but for example, triazine-based, benzotriazole-based, benzophenone-based, cyclic iminoester-based, salicylic acid ester-based, cyanoacrylate-based, etc. can be mentioned. Among these, from the viewpoints of weather resistance and durability, triazine-based, benzotriazole-based, benzophenone-based, and cyclic iminoester-based are more preferred, and triazine-based is even more preferred. These ultraviolet absorbers may be used alone or in combination of two or more kinds. Furthermore, it is also possible to use those in which these compounds are incorporated into a polymer.

[0046] Similarly, in the curable composition, a light stabilizer may be added in order to improve the weather resistance when it becomes a cured product. ​​​​​​​​​It may be contained. The light stabilizer is not particularly limited. For example, amine-based light stabilizers such as phenolic light stabilizers, phosphorus-based light stabilizers, thioether-based light stabilizers, etc. may be mentioned. Among these, amine-based light stabilizers, phenolic light stabilizers, and phosphorus-based light stabilizers are preferred. Considering especially the low yellowing property, etc., amine-based light stabilizers are more preferred. These light stabilizers may be used alone or in combination of two or more. Also, it is possible to use those in which these compounds are incorporated into a polymer.

[0047] The curable composition may further contain a leveling agent in order to improve the appearance of the cured product. Examples of the leveling agent include acrylic leveling agents, silicone leveling agents, fluorine-based leveling agents, etc. These leveling agents may be used alone or in combination of two or more.

[0048] The curable composition may contain particles from the viewpoints of preventing blocking and improving slipperiness when formed into a cured product. The particles may be organic particles or inorganic particles, and two or more kinds may be used in combination. The inorganic particles may be particles surface-modified with a silane coupling agent having a reactive group such as a (meth)acryloyl group.

[0049] Also, the curable composition may contain a polymerization accelerator, an antistatic agent, a plasticizer, an antioxidant, an ultraviolet absorber, an infrared absorber, etc. within a range not impairing the effects of the present invention.

[0050] Furthermore, when applying the curable composition onto a substrate, it is preferable to use an organic solvent as needed for the purpose of improving workability. Examples of organic solvents include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenetole; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; amide solvents such as dimethylformamide, diethylformamide, and N-methylpyrrolidone; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; halogen solvents such as dichloromethane and chloroform; and the like. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, ester solvents, ether solvents, alcohol solvents, and ketone solvents are preferred in terms of easily improving workability in coating.

[0051] The content of the active group in the curable composition is such that the content of the active group derived from the copolymer per 100 g of the nonvolatile content of the curable composition is in the range of 0.1 to 100 mmol / 100 g, more preferably 0.5 A curing reaction can be expected, and it becomes possible to exhibit antifouling properties and liquid repellency. In addition, the content of the active group can be estimated by analysis methods such as NMR and GCMS after the curable composition is separated and purified. It is possible to estimate.

[0052] The content of the polymer having an active group that generates radicals by irradiation with active energy rays in the curable composition is 0.1% by mass or more, preferably 0.2 to 25% by mass, with respect to the non-volatile content, in terms of imparting an uneven structure to the surface of the cured product and improving the active energy ray curability. Preferably 0.2 to 25% by mass, more preferably 0.5 to 20% by mass, still more preferably 1 to 15% by mass, particularly preferably 2 to 12% by mass, and most preferably in the range of 3 to 10% by mass. The non-volatile content of the curable composition is the total mass of components other than solvents such as organic solvents. The ratio of the non-volatile content in the curable composition can be measured by a conventionally known method. For example, when 1 g of the composition is spread out and heated at 100 ° C for 1 hour to volatilize the organic solvent, it can be calculated from the change in weight. It can be calculated from the change in weight.

[0053] The non-polymeric photoinitiator in the curable composition is preferably contained to such an extent that it does not cure preferentially over the polymer having an active group that generates radicals by irradiation with active energy rays. Non- The content of the polymeric photoinitiator is 0.1% by mass or more, preferably 0.2 to 10% by mass, more preferably 0.5 to 8% by mass, still more preferably 1 to 7% by mass %, particularly preferably in the range of 2 to 5% by mass. By setting the above range, it is possible to form surface irregularities while suppressing the irradiation amount of active energy rays to a low level. In addition, it is possible to adjust optical properties such as haze and gloss. While forming, the irradiation amount of active energy rays can be suppressed to a low level. Also, optical properties such as haze and gloss can be adjusted. It is also possible to adjust.

[0054] The content of (meth)acrylate in the curable composition is 0.1 to 99.8% by mass, preferably 10 to 99.6% by mass, more preferably 30 to 99% by mass, still more preferably 50 to 98% by mass, and particularly preferably 70 to 96% by mass, based on the non-volatile content of the curable composition, from the viewpoint of good curability. By using within the above range, the hardness of the cured product becomes sufficient and the scratch resistance is improved. Particularly when it is desired to increase the hardness of the cured product, the (meth)acrylate having 6 or more functional groups is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more. Also, particularly when it is desired to improve the appearance, the (meth)acrylate of the hyperbranched body is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more. In addition, when it is desired to adjust the haze, the glycerin-containing (meth)acrylate is preferably in the range of 5 to 70% by mass, more preferably 10 to 60% by mass, still more preferably 15 to 50% by mass. The solid content concentration of the curable composition can be appropriately changed according to the application, but from the viewpoint of improving the operability in the coating operation, it is preferably 1 to 100%, more preferably 5 to 90%, still more preferably 10 to 80%, and particularly preferably 20 to 70%. <Cured Product> The cured product of the curable composition can be formed, for example, by applying the curable composition onto the surface of a substrate or an article to form a coating film, drying if necessary, and then irradiating the coating film with active energy rays. When forming a cured product (cured film) by coating, the coating method of the curable composition is not particularly limited.

[0055]

[0056] ​​​​​​​​​​​​​​For example, dip coating, air knife coating, curtain coating, spin coating, etc. coating method, roller coating method, bar coating method, wire bar coating method, gravure coating method, The coating can be carried out by a known method such as spray coating.

[0057] When the curable composition contains an organic solvent, it is preferable to heat and dry the composition before irradiating it with active energy rays. It is preferable to heat and dry the coating film in advance to effectively remove the organic solvent from the coating film. The drying temperature for the heat drying is preferably 30 to 200° C., more preferably 40 The drying temperature is preferably from 0.01 to 30 minutes. It is preferable, and 0.1 to 10 minutes is more preferable.

[0058] Examples of active energy rays include ultraviolet rays, electron beams, visible light, infrared rays, and X-rays. Among these, ultraviolet rays and electron beams are preferred from the viewpoints of curing property and prevention of deterioration of the substrate. In addition, the amount of irradiation of the active energy ray is preferably adjusted according to the amount of the active energy ray to be irradiated. The appropriate selection can be made.

[0059] For example, when using ultraviolet light, the total cumulative light intensity is 50 to 3,000 mJ / c. m 2 It is preferable to irradiate so that the irradiation temperature is 100 to 2,000 mJ / cm 2 is more preferred 200~1,000mJ / cm 2 More preferably, the illuminance is 50 to 6 00mW / cm 2 is preferable, and 75 to 450 mW / cm 2 More preferably, 100 to 30 0mW / cm 2 As the light source, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, Lamps, electrodeless lamps, metal halide lamps, or scanning or curtain type electron beam acceleration paths Electron beams, high pressure mercury lamps, ultra-high pressure mercury lamps, low pressure mercury lamps, etc. can be used.

[0060] The thickness of the cured product (cured film) is preferably 0.1 to 20 μm, more preferably 0.2 to 1 The thickness of the cured product is preferably in the range of 0.0 μm, and more preferably in the range of 0.3 to 7 μm. In this way, it is easy to realize a desired uneven surface structure. The thickness of the cured product can be determined by observing a cross section using an electron microscope or the like.

[0061] The haze of the cured product is measured by the method described in the Examples below, depending on the application. Although there is an optimum value and it is difficult to generalize, it is preferably 3% or more, more preferably 5% or more, and even more preferably 10% or more. Preferably, the range is 10% or more, particularly preferably 20% or more, and most preferably 30% or more. There is no particular upper limit, but it is, for example, 99%. For example, strong matte finish or For applications requiring strong anti-glare properties (such as anti-glare films), it is preferably 50% or more. More preferably, 60% or more, and even more preferably, 80% or more, may be required. be.

[0062] The cured product preferably has transparency. The total light transmittance is preferably 40 to 100%, more preferably 60 to 99%, and further preferably The range is preferably 80 to 98%. When the range is equal to or higher than the lower limit, the transparency is excellent. If the content is equal to or less than the upper limit, the film will be suitable for various optical applications, and if the content is equal to or less than the upper limit, the film will have excellent matte properties. do.

[0063] The cured product had a 20° gloss (20° specular light) measured by the method described in the Examples below. The glossiness has an optimal value depending on various applications and cannot be generally stated. Preferably, it is 80 or less, more preferably 60 or less, still more preferably 50 or less, and there is no particular limitation on the lower limit, but for example, it is 0.1 or more. For example, in applications that require strong anti-glare properties and strong anti-reflection properties (such as anti-glare films), it is preferably 20 or less, more preferably 10 or less, and still more preferably 5 or less in some cases where low values are required. Similarly, for the 60° gloss, there is an optimal value depending on various applications and cannot be generally stated. Preferably, it is 120 or less, more preferably 100 or less, still more preferably 80 or less, and there is no particular limitation on the lower limit, but for example, it is 0.1 or more. For example, in applications that require strong anti-glare properties and strong anti-reflection properties (such as anti-glare films), it is preferably 50 or less, more preferably 30 or less, and still more preferably 20 or less in some cases where low values are required. The surface of the cured product is an uneven surface (non-smooth surface) having irregularities. Thereby, the cured product has anti-glare properties, anti-reflection properties, and anti-blocking properties. The arithmetic mean roughness (Ra) of the cured product measured by the method described in the examples below has an optimal value depending on various applications and cannot be generally stated. Preferably, it is 0.01 μm or more, more preferably 0.03 μm or more, still more preferably 0.04 μm or more, and there is no particular limitation on the upper limit, but for example, it is in the range of 2 μm or less. For example, in applications that require strong anti-glare properties and strong anti-reflection properties (such as anti-glare films), it is preferably 0.05 μm or more, more preferably 0.10 μm or more, and still more preferably 0.15 μm or more in some cases where high values are required.

[0064]

[0065] The inclination angle (inner angle) (θα) of the protrusions on the surface unevenness of the cured product affects the matting property and anti-glare property of the cured product. The higher the angle, the higher the matting property and anti-glare property. The angle (θα) of the cured product measured by the method described in the examples below has an optimal value depending on various applications, and cannot be generally stated. Preferably, it is 0.1° or more, more preferably 1.0° or more, still more preferably 2.0° or more, and there is no particular limitation on the upper limit. For example, it is in the range of 30° or less. For example, in applications that require strong matting properties and strong anti-glare properties (such as anti-glare films), preferably 3.0° or more, more preferably 5.0° or more, still more preferably 8.0° or more, etc. high values may be required. It affects the matting property and anti-glare property of the cured product. The higher the angle, the higher the matting property and anti-glare property. The angle (θα) of the cured product measured by the method described in the examples below has an optimal value depending on various applications, and cannot be generally stated. Preferably, it is 0.1° or more, more preferably 1.0° or more, still more preferably 2.0° or more, and there is no particular limitation on the upper limit. For example, it is in the range of 30° or less. For example, in applications that require strong matting properties and strong anti-glare properties (such as anti-glare films), preferably 3.0° or more, more preferably 5.0° or more, still more preferably 8.0° or more, etc. high values may be required. Preferably, it is 0.1° or more, more preferably 1.0° or more, still more preferably 2.0° or more, and there is no particular limitation on the upper limit. For example, it is in the range of 30° or less. Preferably, it is 0.1° or more, more preferably 1.0° or more, still more preferably 2.0° or more, and there is no particular limitation on the upper limit. For example, it is in the range of 30° or less. For example, in applications that require strong matting properties and strong anti-glare properties (such as anti-glare films), preferably 3.0° or more, more preferably 5.0° or more, still more preferably 8.0° or more, etc. high values may be required. For example, in applications that require strong matting properties and strong anti-glare properties (such as anti-glare films), preferably 3.0° or more, more preferably 5.0° or more, still more preferably 8.0° or more, etc. high values may be required. Preferably, it is 3.0° or more, more preferably 5.0° or more, still more preferably 8.0° or more, etc. high values may be required. Preferably, it is 3.0° or more, more preferably 5.0° or more, still more preferably 8.0° or more, etc. high values may be required.

[0066] <Laminate> The laminate of the present invention (hereinafter, also referred to as "the present laminate") has a base material layer and a layer composed of a cured product (cured film) of a curable composition. The present laminate may further have one or more layers selected from the group consisting of a primer layer provided between the base material layer and the cured product, and a back surface functional layer provided on the surface of the base material layer opposite to the cured product side. Also, as long as the effects of the present invention are not impaired, a surface functional layer provided on the surface of the cured product opposite to the base material layer side may be provided. The laminate of the present invention (hereinafter, also referred to as "the present laminate") has a base material layer and a layer composed of a cured product (cured film) of a curable composition. The present laminate may further have one or more layers selected from the group consisting of a primer layer provided between the base material layer and the cured product, and a back surface functional layer provided on the surface of the base material layer opposite to the cured product side. Also, as long as the effects of the present invention are not impaired, a surface functional layer provided on the surface of the cured product opposite to the base material layer side may be provided. Also, as long as the effects of the present invention are not impaired, a surface functional layer provided on the surface of the cured product opposite to the base material layer side may be provided. Also, as long as the effects of the present invention are not impaired, a surface functional layer provided on the surface of the cured product opposite to the base material layer side may be provided.

[0067] (Base material layer) As the base material layer, known ones can be used, such as resin base materials, metal base materials, paper base materials, glass base materials, etc. Among these, from the viewpoint of processability, resin base materials are preferred. As the base material layer, known ones can be used, such as resin base materials, metal base materials, paper base materials, glass base materials, etc. Among these, from the viewpoint of processability, resin base materials are preferred. The resin base material may be a single-layer structure or a multi-layer structure of two or more layers, and is not particularly limited. It is preferable to make the resin base material into a multi-layer structure of two or more layers, give each layer characteristics, and achieve multi-functionalization. The resin base material may be a single-layer structure or a multi-layer structure of two or more layers, and is not particularly limited. It is preferable to make the resin base material into a multi-layer structure of two or more layers, give each layer characteristics, and achieve multi-functionalization.

[0068] As the resin substrate, various resin films (sheets) can be used. For example, triacetyl cellulose film, polyester film, poly(meth)acrylate film, polyolefin film, polycarbonate film, polyimide film, polystyrene film, polyvinyl chloride film, polyvinyl alcohol film, nylon film, poly urethane film, etc. can be mentioned. When this laminate is applied to display use, triacetyl cellulose film, polyester film, poly(meth)acrylate film, polyolefin film, polycarbonate film, polyimide film are preferred. Among these, due to excellent mechanical properties, triacetyl cellulose film, polyester film, poly( meth)acrylate film, polyolefin film are preferred. Furthermore, considering transparency, moldability, and versatility, triacetyl cellulose film or polyester film is more preferred.

[0069] It is also possible to contain particles in the base material layer for the purpose of imparting slipperiness, preventing the occurrence of scratches in each process, and improving anti-blocking properties, or to contain an ultraviolet absorber for improving weather resistance. It is also possible to contain additives other than the above-mentioned particles and ultraviolet absorbers as needed. As the additives, known additives such as antioxidants, antistatic agents, heat stabilizers, lubricants, plasticizers, dyes, pigments, etc. can be used.

[0070] The thickness of the base material layer is not particularly limited. However, for example, if it is in the form of a film, preferably Or it is in the range of 2 to 350 μm, more preferably 5 to 250 μm, still more preferably 10 to 100 μm.

[0071] Also, in order to improve the adhesion between the substrate layer and the cured product of the curable composition, corona treatment or plasma treatment may be performed.

[0072] (Primer layer) The primer layer is provided to impart various functions between the substrate layer and the cured product layer. Examples of the primer layer include an adhesion improvement layer, an antistatic layer, and the like. The primer layer may have a plurality of functions. For example, the adhesion improvement layer may also serve as an antistatic layer.

[0073] In a preferred embodiment, the primer layer is an adhesion improvement layer. If the adhesion between the substrate layer and the cured product is insufficient, the laminate may not be usable depending on the application. By having the adhesion improvement layer, the adhesion between the substrate layer and the cured product is improved, and the laminate can be used for various applications. Examples of the components constituting the primer layer include, for example, polyester resin, acrylic resin, urethane resin, polyvinyl resin (such as polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer), etc. and the like.

[0074] In another preferred embodiment, the primer layer is an antistatic layer. If the primer layer is an antistatic layer, it can reduce the adhesion of dust and the like due to peeling electrification or friction electrification to the outermost surface of the laminate, particularly the outermost surface on the side where the cured product exists with respect to the substrate layer. To make the primer layer an antistatic layer, for example, the primer layer may contain an antistatic agent. Also, the primer layer can be formed by a known method.

[0075] ​(Inner functional layer) The inner functional layer is provided to impart various functions to the surface on the opposite side of the cured product layer of the base material layer. Examples of the inner functional layer include an adhesive layer, an antistatic layer, a refractive index adjusting layer, and an antiblocking layer. etc. The adhesive layer is provided to bond the laminate to various adherends. The antistatic layer is for preventing the adhesion of surrounding dust, etc. caused by peeling electrification or friction electrification to the outermost surface of the laminate, especially the outermost surface on the opposite side of the cured product layer of the base material layer, and defects caused thereby. The refractive index adjusting layer is provided, for example, to improve the total light transmittance of the laminate. The antiblocking layer is provided to reduce the blocking of the laminate. The inner functional layer can be formed by a known method.

[0076] (Surface functional layer) The surface functional layer can be provided to impart various functions to the surface on the opposite side of the base material layer side of the cured product layer (cured film). Examples of the surface functional layer include an antifouling layer, an antistatic layer, a refractive index adjusting layer (antireflection layer, low reflection layer, etc.), an infrared absorption layer, an ultraviolet absorption layer, and a color correction layer. The surface functional layer can be formed by a known method.

[0077] It is also possible to provide it to further improve the performance of the cured product of the present invention. For example, by forming a surface functional layer with a high content ratio of a fluorine compound, higher antifouling properties and liquid repellency can be imparted. It is also a preferable form to make it a curable surface functional layer to impart durability, and further, by making the fluorine compound contain an active energy ray curable site, it is also possible to make a surface functional layer with higher performance.

Examples

[0078] ​​​​​​​​​​​​ Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The measurement method and evaluation method used in the present invention are as follows.

[0079] (1) Weight-average molecular weight (Mw) The weight-average molecular weight of the copolymer was measured by GPC under the following conditions. Equipment: "e2695" manufactured by Waters Column: "TSKgel Super H3000 + H4000 + H 6000" manufactured by Tosoh Corporation Detector: Differential refractive index detector (RI detector / built-in) Solvent: Tetrahydrofuran Temperature: 40 °C Flow rate: 0.5 mL / min Injection volume: 10 μL Concentration: 0.2 mass% Calibration sample: Monodisperse polystyrene Calibration method: Polystyrene conversion.

[0080] (2) UV irradiation dose (mJ / cm 2 ) In the method described in Example 1 below, in an air atmosphere, a high-pressure mercury lamp was used to irradiate with ultraviolet light repeatedly at an integrated light quantity of 100 mJ / cm 2 and an illuminance of 100 mW / cm 2 . The evaluation was performed based on the integrated light quantity at the time when the coating film was cured (became tack-free). In Examples 12 to 14, repeated irradiation was performed with an integrated light quantity of 50 mJ / cm 2 .

[0081] (3) Measurement of total light transmittance and haze A laminate having a cured layer formed on a triacetyl cellulose film was used as the measurement target. The total light ​The linear transmittance and haze were measured at a wavelength of 550 nm using a haze meter "SH7000" manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS Z 8722 (Geometric Conditions for Irradiation and Light Reception of Transparent Objects), JIS K 7361-1 (Plastics - Test Method for Total Light Transmittance of Transparent Materials) and J IS K 7136 (Plastics - Method for Determining Haze of Transparent Materials). The haze of the laminate is the percentage of transmitted light that has deviated by more than 0.044 rad (2.5°) from the incident light due to forward scattering among the transmitted light that enters from the outermost surface on the side where the cured layer exists with respect to the base material layer and passes through the laminate. (Ratio of diffuse transmittance to total light transmittance). That is, it is the percentage of the transmitted light that has deviated by more than 0.044 rad (2.5°) from the incident light due to forward scattering among the transmitted light that enters from the outermost surface on the side where the cured layer exists with respect to the base material layer and passes through the laminate. (Ratio of diffuse transmittance to total light transmittance). When it is desired to evaluate the haze of the cured product itself, it can be obtained by subtracting the haze value of the base material without the cured product from the haze value of the laminate with the cured product laminated. Specifically, it can be obtained by subtracting the haze value of Comparative Example 1. it can be obtained by subtracting the haze value of Comparative Example 1. In addition, when it is desired to evaluate the haze of the cured product itself, it can be obtained by subtracting the haze value of the base material without the cured product from the haze value of the laminate with the cured product laminated. Specifically, it can be obtained by subtracting the haze value of the base material without the cured product from the haze value of the laminate with the cured product laminated. Specifically, it can be obtained by subtracting the haze value of Comparative Example 1.

[0082] (4) Measurement of 20° and 60° gloss The laminate with the cured film formed on the base material was used as the measurement object. The 20° and 60° gloss (20° and 60° specular glossiness) was measured in accordance with JIS Z 8741-1997 using a gloss meter "VG2000" manufactured by Nippon Denshoku Industries Co., Ltd. The laminate with the cured film formed on the base material was used as the measurement object. The 20° and 60° gloss (20°

[0083] (5) Measurement of the arithmetic mean roughness (Ra) and the inclination angle (inner angle) (θα) of the protrusions of the surface uneven structure The arithmetic mean roughness (Ra) and the inclination angle (inner angle) (θα) of the protrusions of the surface uneven structure of the cured product were measured using a surface shape measurement system (scanning white light interference microscope "VS1330" manufactured by Hitachi High-Technologies Corporation). The magnification of the objective lens at the time of measurement was set to 20 times. On the uneven layer surface, the surface uneven structure in a region of 236.87 μm × 177.60 μm was measured. Measured by the optical interference method, complemented and baseline-corrected, and calculated the arithmetic mean roughness Ra and θα of the uneven cross-section. And θα were calculated.

[0084] (Synthesis Example 1: Synthesis of 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate) Methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was distilled under reduced pressure, and the fraction with a purity of 99.8% or more was collected to obtain a distillate of methacrylic anhydride. The distillation under reduced pressure was carried out by gradually raising the temperature from room temperature to 90 °C at a pressure of 30 Pa. Separately, 22.4 g (0.1 mol) of 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30.4 g (0.3 mol) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 500 mL of methylene chloride (manufactured by Tokyo Chemical Industry Co., Ltd.). To this, 23.1 g (0.15 mol) of the above-mentioned distillate of methacrylic anhydride was added dropwise at room temperature, and the mixture was stirred for 12 hours. The obtained reaction solution was washed three times with 500 mL of ion-exchanged water, and then the organic phase was concentrated to distill off the solvent. The residue was purified by column chromatography (ethyl acetate / hexane = 10 / 90 (volume ratio)) to obtain 21.6 g of the target compound (yield 74%). It was confirmed by 1H-NMR analysis that the obtained compound was 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate. 1H NMR (300 MHz, chloroform-d): δ 8.06 (d, J = 9.0 Hz, 2H), 6.96 (d, J = 9.0 Hz, 2H), 6.13 (d, J = 0.6 Hz, 1H), etc. Hz, 1H), etc. 1 By 1H-NMR analysis, it was confirmed that the obtained compound was 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate. 1 1H NMR (300 MHz, chloroform-d): δ 8.06 (d, J = 9.0 Hz, 2H), 6.96 (d, J = 9.0 Hz, 2H), 6.13 (d, J = 0.6 Hz, 1H), etc. Hz, 1H), 5.59 (s, 1H), 4.50 (d, J = 5.1 Hz, 2H), 4.2 9 (dd, J = 5.5, 4.1 Hz, 3H), 1.94 (dd, J = 1.6, 1.0 Hz , 3H), 1.61 (s, 6H).

[0085] (Production Example 1: Production of a polymer having an active group that generates radicals upon irradiation with active energy rays ( A)) Into a flask equipped with a stirrer, a cooling tube, and a thermometer, 70 parts of methyl isobutyl ketone (hereinafter referred to as M IBK) was placed. Next, the inside of the flask was purged with nitrogen and heated to 65 °C, and 2- [4-(2-Hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methac rylate 38 parts by mass, 1H,1H,7H-dodecafluoromethyl methacrylate 45 parts by mass , 10 parts by mass of 2-hydroxyethyl methacrylate, 7 parts by mass of glycidyl methacrylate , 3 parts by mass of 1-dodecanethiol (nDM) as a chain transfer agent, 2 as a polymerization initiator ,2'-azobis(2,4-dimethylvaleronitrile) (AMBN) 1 part by mass, and MI A mixed solution of 78 parts by mass of BK was added dropwise over 2 hours. Further, after 2 hours, to increase the polymerization rate , 0.5 part by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 0 of MIBK .6 parts by mass of the mixed solution was added and held for 5 hours. Then, the reaction solution was cooled to 40 °C to obtain a MIBK solution (A) of the polymer. Hereinafter, the solid content in solution (A) is referred to as polymer (A). The solid content (non-volatile content) of solution (A) was 40% by mass. Also, the content of active groups per 1 g of polymer (A) was 1.3 mmol / g. The weight average molecular weight (Mw) was 1 10,900.

[0086] (Production of a curable composition (coating solution))​​ The respective materials shown in Table 1 were mixed so as to have the ratios (parts by mass) shown in Table 1 on a non-volatile content basis. . Thereafter, a mixed solvent of propylene glycol monomethyl ether acetate (hereinafter, PMA) and methoxybutanol (PMA:methoxybutanol (mass ratio) being 7:3) was added so that the solid content concentration became 40% by mass, and the mixture was stirred until it became uniform to obtain a curable composition (coating solution). was obtained. · Non-polymeric photoinitiator 1-hydroxycyclohexyl phenyl ketone: B1 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benz dyl]phenyl}-2-methylpropan-1-one: B2 2,2-dimethoxy-2-phenylacetophenone: B3 · (Meth)acrylate Hexafunctional urethane (meth)acrylate: manufactured by Mitsubishi Chemical Corporation, Violet Light (registered trademark) UV-1700B: C1 Hexafunctional hyperbranched (meth)acrylate: Sartomer (registered trademark) CN2303 manufactured by ARKEMA C2 Trifunctional glycerin triacrylate: manufactured by Toagosei Co., Ltd., Aronix (registered trademark ) M-930: C3

[0087] [Example 1] The obtained curable composition was applied to a triacetyl cellulose film (TD80UL manufactured by Fuji Film Co., Ltd.) having a thickness of 80 μm so that the film thickness after drying became 5 μm, and the obtained coating film was dried for 60 seconds with a hot air dryer heated to 70 °C to volatilize the solvent. In an air atmosphere, ultraviolet rays were irradiated 6 times at an integrated light amount of 100 mJ / cm 2 and an illuminance of 100 mW / cm 2 using a high-pressure mercury lamp (600 mJ / cm 2 ​​​​​) A laminate in which a layer made of a cured product is laminated on a film substrate was obtained. For the obtained laminate, the items shown in Table 2 were measured or evaluated by the above method. The results are shown in Table 2. As shown, when the ultraviolet irradiation dose was 100 mJ / cm 2 , it cured. The haze, gloss, Ra , and θα showed good results.

[0088] [Examples 2 to 11] In Example 1, except that the coating liquid composition was changed to the coating liquid composition shown in Table 1, it was produced in the same manner as in Example 1 to obtain a laminate having a cured film. The properties of the obtained laminate are shown in Table 2 below .

[0089] [Examples 12 to 14] In Example 1, the coating liquid composition was changed to the coating liquid composition shown in Table 1, and the integrated light quantity was 50 mJ / cm 2 , and the illuminance was 100 mW / cm 2 . The ultraviolet light was irradiated 12 times (600 mJ / cm 2 ). Except for this, it was produced in the same manner as in Example 1 to obtain a laminate having a cured film. The properties of the obtained laminate are shown in Table 2 below.

[0090] [Comparative Example 1] In Example 1, a triacetyl cellulose film (manufactured by Fuji Film Co., TD80UL) was evaluated without laminating a cured film. The properties are shown in Table 2 below. [Comparative Examples 2 to 9] In Example 1, except that the coating liquid composition was changed to the coating liquid composition shown in Table 1, it was produced in the same manner as in Example 1 to obtain a laminate having a cured film. The properties of the obtained laminate are shown in Table 2 below . Note that in Comparative Example 2, it did not cure with 6 irradiations, so it is the evaluation result of the laminate that was irradiated 11 times until it cured . Moreover, Comparative Example 10 did not cure after six irradiations.

[0091]

Table 1

[0092]

Table 2

Claims

1. A curable composition containing a polymer having an active group that generates radicals upon irradiation with active energy rays, a non-polymeric photoinitiator, and (meth)acrylate.

2. The active group that generates radicals upon irradiation with the active energy rays is an α-hydroxyket one group, benzophenone group, acetophenone group, benzoin group, α-aminoketone group, α- diketone group, α-diketone dialkyl acetal group, anthraquinone group, thioxanthone group, and phosphine oxide group, and the curable composition according to claim 1, which is one or more selected from the group consisting of curable composition.

3. The polymer having an active group that generates radicals upon irradiation with the active energy rays is a per fluoroalkylene group or a (meth)acrylate alkyl ester having an alkyl group having 4 or more carbon atoms, and the curable composition according to claim 1, which contains a structural unit derived from alkyl ester.

4. The weight average molecular weight of the polymer having an active group that generates radicals upon irradiation with the active energy rays is 1,000 to 500,000, and the curable composition according to claim 3. curable composition.

5. The molecular weight of the non-polymeric photoinitiator is less than 1,000, and the curable composition according to claim 1.

6. The non-polymeric photoinitiator is an alkylphenone type or a benzyl ketal type, and the curable composition according to claim 1.

7. The (meth)acrylate is trifunctional or higher, and the curable composition according to claim 1.

8. The (meth)acrylate contains any one or more of urethane acrylate, (meth)acrylate of a hyperbranched body, or glycerin-containing (meth)acrylate, and the curable composition according to claim 7. curable composition.

9. A cured product obtained by curing the curable composition according to claim 1 or 5.

10. The cured product is a film-like material having an uneven structure on the surface, and the cured product according to claim 9. cured product.

11. The haze of the cured product is 3% or more, and the cured product according to claim 10.

12. The 20° gloss of the cured product is 80 or less, and the cured product according to claim 10.

13. The arithmetic mean roughness (Ra) of the cured product is 0.01 μm or more, and the cured product according to claim 10.

14. A curable composition containing a polymer having an active group that generates radicals upon irradiation with active energy rays, a non-polymeric photoinitiator, and (meth)acrylate is formed into a coating film, and the former A method for producing a cured product by irradiating an active energy ray on a recording film.

15. A laminate in which the cured product according to claim 9 is laminated on a substrate surface.

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